Styroflex/polyaniline (STF/PAni) blends were prepared by two routes namely by in situ and thermo mechanical processing method with various PAni compositions, namely, 0, 15, 30, and 45 wt %. The influence of volume fraction of PAni in the blends and synthetic routes of the STF/PAni blends on the volume resistivity and microcrystalline parameters have been investigated. The microcrystalline parameters such as the nanocrystal size (), lattice disorder (g), interplanar distance (d hkl ), width of the crystallite size distribution, surface weighted crystal size (D s ), and crystallite area were evaluated from the wide angle X-ray scattering profiles. The different asymmetric column length distribution functions namely, exponential, reinhold, and lognormal distribution methods were employed to probe the microcrystalline behavior of the STF/PAni blends and the results are compared.